Reactive polyoxazolines having a perfluorinated group

ABSTRACT

A compound of the formula: (I) wherein: R 1  is selected from H, an alkyl group, an aryl group, and combinations thereof; R 2  is R f —Y—(CH 2 )X—; R 3  is a reactive group; R f  is a perfluorinated alkyl group; Y is selected from a bond, S(O) 2 —N(CH 3 )—, —S(O) 2 —N(CH 2 CH 3 )—, —S(O) 2 —O— —S(O) 2 — —C(O)—, —C(O)—S— —C(O)—O— —C(O)—NH—, —C(O)—N(CH 3 )—, —C(O)—N(CH 2 CH 3 )—, —(CH 2 CH 2 )y-, —O—, and —O—C(O)—CH═CH—C(O)—O—; n is greater than 10; x is 2 to 20; and y is at least 1.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional PatentApplication No. 61/739,150, filed Dec. 19, 2012, the disclosure of whichis incorporated by reference herein in its entirety.

BACKGROUND

Surfaces that possess unique wetting behavior, such assuperhydrophilicity (surfaces having water contact angles of less than5°) or amphiphilicity (surfaces having affinity to both hydrophilic andhydrophobic media) are desirable for a number of applications. Forinstance, surfaces that resist fogging are needed for windshields,safety glasses, and other eyewear. Fog forms when water condenses on amaterial and beads up to form micron-sized droplets that scatter light,resulting in haziness. Superhydrophilic surfaces often resist fogformation because any condensing water instantly wets the surface toform a transparent thin film rather than individual droplets. However,the anti-fogging properties of these surfaces can be masked byenvironmental contamination. Thus, surfaces that exhibit easy removal ofcontamination from grease or dust can help retain anti-fog propertiesfor prolonged exposure times.

The need for easy-to-clean (i.e., easy clean) and anti-fogging surfacesis therefore driving the development of new amphiphilic polymers withreactive groups that can be formulated into robust, durable coatings.

SUMMARY

The present disclosure provides reactive polyoxazolines (POx) having aperfluorinated alkyl group. More specifically, the disclosure providesnovel amphiphilic polymerizable polymers, where polyoxazolines areemployed as the hydrophilic component, and a perfluorinated alkyl groupis employed as the hydrophobic component. Such polymerizable polymersare suitable for use in making amphiphilic polymers that are useful inmaking anti-fog, anti-fouling, and/or easy clean coatings.

In one embodiment, the present disclosure provides a compound of theformula:

wherein: R¹ is selected from H, an alkyl group, an aryl group, andcombinations thereof; R² is R^(f)—Y—(CH₂)_(x)—; R³ is a reactive group;R^(f) is a perfluorinated alkyl group; Y is selected from a bond,—S(O)₂—N(CH₃)—, —S(O)₂—N(CH₂CH₃)—, —S(O)₂—O—, —S(O)₂—, —C(O)—, —C(O)—S—,—C(O)—O—, —C(O)—NH—, —C(O)—N(CH₃)—, —C(O)—N(CH₂CH₃)—, —(CH₂CH₂O)_(y)—,—O—, and —O—C(O)—CH═CH—C(O)—O—; n is an integer of greater than 10; x isan integer from 2 to 20; and y is an integer of at least 1.

In one embodiment, the present disclosure provides a compound of theformula:

wherein: R¹ is selected from H, an alkyl group, an aryl group, andcombinations thereof; R² is R^(f)—Y—(CH₂)_(x)—; R³ is a reactive groupselected from a polymerizable group and a group of formula —W—Si(R⁹)₃;R^(f) is a perfluorinated alkyl group; Y is selected from a bond,—S(O)₂—N(CH₃)—, —S(O)₂—N(CH₂CH₃)—, —S(O)₂—O—, —S(O)₂—, —C(O)—, —C(O)—S—,—C(O)—O—, —C(O)—NH—, —C(O)—N(CH₃)—, —C(O)—N(CH₂CH₃)—, —(CH₂CH₂O)_(y)—,—O—, and —O—C(O)—CH═CH—C(O)—O—; n is an integer of greater than 10; x isan integer from 2 to 20; y is an integer of at least 1; W is an organicgroup; and each R⁹ is independently an alkyl group, aryl group, acombination thereof, or a hydrolyzable group, wherein at least one R⁹ isa hydrolyzable group.

In one embodiment, the present disclosure provides a compound of theformula:

wherein: R¹ is selected from H, an alkyl group, an aryl group, andcombinations thereof; R² is R^(f)—Y—(CH₂)_(x)—; R³ is a reactive groupselected from a vinyl group, a vinylether group, a (meth)acryloyloxygroup, a (meth)acryloylamino group, a trialkoxysilylalkylthio group, anda trialkoxysilylalkylamino group; R^(f) is a perfluorinated (C1-C5)alkylgroup; Y is selected from a bond, —S(O)₂—N(CH₃)—, —C(O)—NH—, and—(CH₂CH₂O)_(y)—; n is an integer from 20 to 100; x is an integer from 2to 20; and y is an integer from 1 to 20.

As used herein, the term “organic group” means a hydrocarbon group (withoptional elements other than carbon and hydrogen, such as oxygen,nitrogen, sulfur, silicon, and halogens) that is classified as analiphatic group, cyclic group, or combination of aliphatic and cyclicgroups (e.g., alkaryl and aralkyl groups). In the context of the presentinvention, the organic groups are those that do not interfere with theformation of the reactive polyoxazoline. The term “aliphatic group”means a saturated or unsaturated linear or branched hydrocarbon group.This term is used to encompass alkyl, alkenyl, and alkynyl groups, forexample. The term “alkyl group” is defined herein below. The term“alkenyl group” means an unsaturated, linear or branched hydrocarbongroup with one or more carbon-carbon double bonds, such as a vinylgroup. The term “alkynyl group” means an unsaturated, linear or branchedhydrocarbon group with one or more carbon-carbon triple bonds. The term“cyclic group” means a closed ring hydrocarbon group that is classifiedas an alicyclic group, aromatic group, or heterocyclic group. The term“alicyclic group” means a cyclic hydrocarbon group having propertiesresembling those of aliphatic groups. The term “aromatic group” or “arylgroup” are defined herein below. The term “heterocyclic group” means aclosed ring hydrocarbon in which one or more of the atoms in the ring isan element other than carbon (e.g., nitrogen, oxygen, sulfur, etc.). Theorganic group can have any suitable valency but is often monovalent ordivalent.

The term “alkyl” refers to a monovalent group that is a radical of analkane and includes straight-chain, branched, cyclic, and bicyclic alkylgroups, and combinations thereof, including both unsubstituted andsubstituted alkyl groups. Unless otherwise indicated, the alkyl groupstypically contain from 1 to 30 carbon atoms. In some embodiments, thealkyl groups contain 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. Examples ofalkyl groups include, but are not limited to, methyl, ethyl, n-propyl,n-butyl, n-pentyl, isobutyl, t-butyl, isopropyl, n-octyl, n-heptyl,ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl,and the like.

The term “alkylene” refers to a divalent group that is a radical of analkane and includes groups that are linear, branched, cyclic, bicyclic,or a combination thereof. Unless otherwise indicated, the alkylene grouptypically has 1 to 30 carbon atoms. In some embodiments, the alkylenegroup has 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbonatoms, or 1 to 4 carbon atoms. Examples of alkylene groups include, butare not limited to, methylene, ethylene, 1,3-propylene, 1,2-propylene,1,4-butylene, 1,4-cyclohexylene, and 1,4-cyclohexyldimethylene.

The term “alkoxy” refers to a monovalent group having an oxy groupbonded directly to an alkyl group.

The term “aryl” refers to a monovalent group that is aromatic and,optionally, carbocyclic. The aryl has at least one aromatic ring. Anyadditional rings can be unsaturated, partially saturated, saturated, oraromatic. Optionally, the aromatic ring can have one or more additionalcarbocyclic rings that are fused to the aromatic ring. Unless otherwiseindicated, the aryl groups typically contain from 6 to 30 carbon atoms.In some embodiments, the aryl groups contain 6 to 20, 6 to 18, 6 to 16,6 to 12, or 6 to 10 carbon atoms. Examples of an aryl group includephenyl, naphthyl, biphenyl, phenanthryl, and anthracyl.

The term “arylene” refers to a divalent group that is aromatic and,optionally, carbocyclic. The arylene has at least one aromatic ring. Anyadditional rings can be unsaturated, partially saturated, or saturated.Optionally, an aromatic ring can have one or more additional carbocyclicrings that are fused to the aromatic ring. Unless otherwise indicated,arylene groups often have 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6to 16 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms.

The term “aralkyl” refers to a monovalent group that is an alkyl groupsubstituted with an aryl group (e.g., as in a benzyl group). The term“alkaryl” refers to a monovalent group that is an aryl substituted withan alkyl group (e.g., as in a tolyl group). Unless otherwise indicated,for both groups, the alkyl portion often has 1 to 10 carbon atoms, 1 to6 carbon atoms, or 1 to 4 carbon atoms and an aryl portion often has 6to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 16 carbon atoms, 6 to 12carbon atoms, or 6 to 10 carbon atoms.

The term “aralkylene” refers to a divalent group that is a an alkylenegroup substituted with an aryl group or an alkylene group attached to anarylene group. The term “alkarylene” refers to a divalent group that isan arylene group substituted with an alkyl group or an arylene groupattached to an alkylene group. Unless otherwise indicated, for bothgroups, the alkyl or alkylene portion typically has from 1 to 20 carbonatoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbonatoms. Unless otherwise indicated, for both groups, the aryl or aryleneportion typically has from 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6to 16 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms.

The term “perfluorinated alkyl group” or “perfluoroalkyl group” refersto an alkane group having all C—H bonds replaced with C—F bonds.

The term “silyl” refers to a monovalent group of formula —Si(R^(c))₃where R^(c) is a hydrolyzable group or a non-hydrolyzable group. In manyembodiments, the silyl group is a “hydrolyzable silyl” group, whichmeans that the silyl group contains at least one R^(c) group that is ahydrolyzable group.

The term “hydrolyzable group” refers to a group that can react withwater having a pH of 1 to 10 under conditions of atmospheric pressure.The hydrolyzable group is often converted to a hydroxyl group when itreacts. The hydroxyl group often undergoes further reactions. Typicalhydrolyzable groups include, but are not limited to, alkoxy, aryloxy,aralkyloxy, alkaryloxy, acyloxy, or halo. As used herein, the term isoften used in reference to one of more groups bonded to a silicon atomin a silyl group.

The term “non-hydrolyzable group” refers to a group that cannot reactwith water having a pH of 1 to 10 under conditions of atmosphericpressure. Typical non-hydrolyzable groups include, but are not limitedto, alkyl, aryl, aralkyl, and alkaryl. As used herein, the term is oftenused in reference to one or more groups bonded to a silicon atom in asilyl group.

The term “alkoxy” refers to a monovalent group having an oxy groupbonded directly to an alkyl group.

The term “aryloxy” refers to a monovalent group having an oxy groupbonded directly to an aryl group.

The terms “aralkyloxy” and “alkaryloxy” refer to a monovalent grouphaving an oxy group bonded directly to an aralkyl group or an alkarylgroup, respectively.

The term “acyloxy” refers to a monovalent group of the formula—O(CO)R^(b) where R^(b) is alkyl, aryl, aralkyl, or alkaryl. Suitablealkyl R^(b) groups often have 1 to 10 carbon atoms, 1 to 6 carbon atoms,or 1 to 4 carbon atoms. Suitable aryl R^(b) groups often have 6 to 12carbon atoms such as, for example, phenyl. Suitable aralkyl and alkarylR^(b) groups often have an alkyl group with 1 to 10 carbon atoms, 1 to 6carbon atoms, or 1 to 4 carbon atoms and an aryl having 6 to 12 carbonatoms.

The term “halo” refers to a halogen atom such as fluoro, bromo, iodo, orchloro. When part of a reactive silyl, the halo group is often chloro.

The term “reactive group” refers to a functionality that will react withitself and/or another molecule (e.g., through polymerizing orcrosslinking) to form a polymeric network. Such group can also bereferred to as a “polymerizable group.” The polymerizable group oftenincludes a group that can undergo a free radical reaction such as anethylenically unsaturated group. Alternatively, the polymerizable groupcan undergo a hydrolysis and/or condensation reaction. Suchpolymerizable groups include hydrolyzable silyl groups. Additionally,the term “reactive group” refers to a first group that can react with asecond group on a substrate surface to attach the first group tosubstrate though the formation of a covalent bond. Such group can alsobe referred to as a “substrate-reactive group.” The substrate-reactivegroup typically includes a hydrolyzable silyl group.

The term “(meth)acryloyloxy group” includes an acryloyloxy group(—O—(CO)—CH═CH₂) and a methacryloyloxy group (—O—(CO)—C(CH₃)═CH₂).

The term “(meth)acryloylamino group” includes an acryloylamino group(—NR—(CO)—CH═CH₂) and a methacryloylamino group (—NR—(CO)—C(CH₃)═CH₂)including embodiments wherein the amide nitrogen is bonded to ahydrogen, methyl group, or ethyl group (R is H, methyl, or ethyl).

The terms “comprises” and variations thereof do not have a limitingmeaning where these terms appear in the description and claims.

The words “preferred” and “preferably” refer to embodiments of thedisclosure that may afford certain benefits, under certaincircumstances. However, other embodiments may also be preferred, underthe same or other circumstances. Furthermore, the recitation of one ormore preferred embodiments does not imply that other embodiments are notuseful, and is not intended to exclude other embodiments from the scopeof the disclosure.

In this application, terms such as “a,” “an,” and “the” are not intendedto refer to only a singular entity, but include the general class ofwhich a specific example may be used for illustration. The terms “a,”“an,” and “the” are used interchangeably with the term “at least one.”The phrases “at least one of” and “comprises at least one of” followedby a list refers to any one of the items in the list and any combinationof two or more items in the list.

As used herein, the term “or” is generally employed in its usual senseincluding “and/or” unless the content clearly dictates otherwise. Theterm “and/or” means one or all of the listed elements or a combinationof any two or more of the listed elements.

Also herein, all numbers are assumed to be modified by the term “about”and preferably by the term “exactly.” As used herein, in connection witha measured quantity, the term “about” refers to that variation in themeasured quantity as would be expected by the skilled artisan making themeasurement and exercising a level of care commensurate with theobjective of the measurement and the precision of the measuringequipment used.

Also herein, the recitations of numerical ranges by endpoints includeall numbers subsumed within that range as well as the endpoints (e.g., 1to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

When a group is present more than once in a formula described herein,each group is “independently” selected, whether specifically stated ornot. For example, when more than one R group is present in a formula,each R group is independently selected. Furthermore, subgroups containedwithin these groups are also independently selected. For example, wheneach R group contains a Y group, each Y is also independently selected.

As used herein, the term “room temperature” refers to a temperature of20° C. to 25° C. or 22° C. to 25° C.

The above summary of the present disclosure is not intended to describeeach disclosed embodiment or every implementation of the presentdisclosure. The description that follows more particularly exemplifiesillustrative embodiments. In several places throughout the application,guidance is provided through lists of examples, which examples can beused in various combinations. In each instance, the recited list servesonly as a representative group and should not be interpreted as anexclusive list.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

The present disclosure provides reactive polyoxazolines (POx) having aperfluorinated alkyl group.

In recent years, the use of polyoxazolines (POx) in biomedicalapplications has gained interest due to their high biocompatibility andstealth behavior that resembles polyethylene glycol (PEG). POx's can beobtained through living cationic ring opening polymerization, whichprovides an easy access to a wide variety of well-defined polymers.Furthermore, the functionality and the resulting physical properties ofPOx's can be tuned simply by changing the initiator, monomer, and theend-group used in the polymerization. Poly(methyl-oxazoline)s andpoly(ethyl-oxazoline)s have been shown to have faster in-vivo clearanceand in the case of poly(methyl-oxazoline) more hydrophilic characterthan PEG, which brings a great advantage for antifouling applications.Polyoxazolines also have improved chemical stability, allowing for theproduction of more durable coatings than those including PEG.

The present disclosure provides reactive polyoxazolines (POx) having aperfluorinated alkyl group. The polyoxazolines are employed as thehydrophilic component, and a perfluorinated alkyl group is employed asthe hydrophobic component. Such amphiphilic polymerizable polymers aresuitable for making polymers that can be used in making antifoulingcoatings.

In one embodiment, the present disclosure provides a compound (i.e.,polymerizable or substrate-reactive polyoxazoline) of the formula:

In certain embodiments, R¹ is selected from H, an alkyl group, an arylgroup, and combinations thereof. In certain embodiments, R¹ is H, a(C1-C20)alkyl group, a (C6-C12)aryl group, a (C6-C12)ar(C1-C20)alkylgroup, or a (C1-C20)alk(C6-C12)aryl group. In certain embodiments, R¹ isselected from H, methyl, and ethyl.

In certain embodiments, R² is R^(f)—Y—(CH₂)_(x)—.

In certain embodiments, R³ is a reactive group (e.g., a polymerizablegroup and/or a substrate-reactive group).

In certain embodiments, R³ is a polymerizable group, in particular anethylenically unsaturated group selected from a vinyl group, avinylether group, a (meth)acryloyloxy group, and a (meth)acryloylaminogroup (including embodiments wherein the nitrogen is optionallysubstituted with methyl or ethyl).

In certain embodiments, R³ is a substrate-reactive group (e.g., anorganic group containing a hydrolyzable silyl group) that providesfunctionality for bonding to a substrate surface.

In certain embodiments R³ is of the formula —W—Si(R⁹)₃ wherein W is anorganic group and each R⁹ group is independently selected from an alkylgroup, an aryl group, or a combination thereof (an alkaryl group or anaralkyl group) and a hydrolyzable group; and at least one R⁹ is ahydrolyzable group. In certain embodiments, the hydrolyzable group isselected from a halo, an alkoxy group, and an acyloxy group. In certainembodiments, the hydrolyzable group is selected from a halo, a(C1-C4)alkoxy group, and a (C1-C4)acyloxy group. In certain embodiments,all three R⁹ groups are hydrolyzable groups. In certain embodiments, allthree R⁹ groups are the same.

In certain embodiments, W is selected from an alkylene group, an arylenegroup, and a combination thereof (i.e., an alkarylene group or anaralkylene group), optionally including —O—, —C(O)—, —NR—, —S—, or acombination thereof, wherein R is H, methyl, or ethyl. Such optionalgroup is typically not directly bonded to the silyl group. In certainembodiments, W is selected from a (C1-C20)alkylene group, a(C6-C12)arylene group, and combination thereof, optionally including—O—, —C(O)—, —NR—, —S—, or a combination thereof. For example, W can beof the divalent group of formula —N(R)—R⁷ or —S—R⁸— where R⁷ and R⁸ areeach an alkylene group and R is H, methyl, or ethyl.

Examples substrate-reactive groups include trialkoxysilylalkylamino(including embodiments wherein the nitrogen is optionally substitutedwith methyl or ethyl) and trialkoxysilylalkylthio. Such groups are notonly substrate-reactive but may also be polymerizable and form anetwork.

In certain embodiments, R³ is selected from a (meth)acryloyloxy group, a(meth)acryloylamino group, a trialkoxysilylalkylthio group, and atrialkyoxysilylalkylamino group.

In certain embodiments, R³ is selected from a (meth)acryloyloxy group,and a (meth)acryloylamino group.

In certain embodiments, the trialkoxysilylalkylamino group is of theformula —N(R)—R⁷—Si(OR⁴)(OR⁵)(OR⁶), wherein R is H, methyl, or ethyl,and each R⁴, R⁵, and R⁶ is an alkyl group, and R⁷ is an alkylene group.In certain embodiments, the trialkoxysilylalkylamino group is of theformula —N(R)—CH₂CH₂CH₂—Si(OR⁴)(OR⁵)(OR⁶), wherein R is H, methyl, orethyl, and each R⁴, R⁵, and R⁶ is an alkyl group, preferably methyl orethyl.

In certain embodiments, the trialkoxysilylalkylthio group is of theformula —S—R—Si(OR⁴)(OR⁵)(OR⁶), wherein each R⁴, R⁵, and R⁶ is an alkylgroup, and R⁸ is an alkylene group. In certain embodiments, thetrialkoxysilylalkylthio is of the formula —S—CH₂CH₂CH₂—Si(OR⁴)(OR)(OR⁶),wherein R is H, methyl, or ethyl, and each R⁴, R⁵, and R⁶ is an alkylgroup, preferably methyl or ethyl.

In certain embodiments, R² is R^(f)—Y—(CH₂)_(x)—. Y is selected from abond, —S(O)₂—N(CH₃)—, —S(O)₂—N(CH₂CH₃)—, —S(O)₂—O—, —S(O)₂—, —C(O)—,—C(O)—S—, —C(O)—O—, —C(O)—NH—, —C(O)—N(CH₃)—, —C(O)—N(CH₂CH₃)—,—(CH₂CH₂O)_(y)—, —O—, and —O—C(O)—CH═CH—C(O)—O—. In certain embodiments,Y is selected from a bond, —S(O)₂—N(CH₃)—, —C(O)—NH—, and—(CH₂CH₂O)_(y)—.

In certain embodiments, R^(f) is a perfluorinated alkyl group. Incertain embodiments, R^(f) is a perfluorinated (C1-C5)alkyl group. Incertain embodiments, R^(f) is a perfluorinated C4 alkyl group.

In certain embodiments, n is an integer of greater than 10. In certainembodiments, n is no greater than 500. In certain embodiments, n is 20to 100.

In certain embodiments, x is an integer from 2 to 20. In certainembodiments, x is 2 to 10. In certain embodiments, x is 2 to 6.

In certain embodiments, y is an integer equal to at least 1. In certainembodiments, y is no greater than 20. In certain embodiments, y is 1 to5.

In one embodiment, the present disclosure provides a compound (i.e., apolymerizable or substrate-reactive polyoxazoline) of the formula:

wherein: R¹ is selected from H, an alkyl group, an aryl group, andcombinations thereof; R² is R^(f)—Y—(CH₂)_(x)—; R³ is a reactive group;R^(f) is a perfluorinated alkyl group; Y is selected from a bond,—S(O)₂—N(CH₃)—, —S(O)₂—N(CH₂CH₃)—, —S(O)₂—O—, —S(O)₂—, —C(O)—, —C(O)—S—,—C(O)—O—, —C(O)—NH—, —C(O)—N(CH₃)—, —C(O)—N(CH₂CH₃)—, —(CH₂CH₂O)_(y)—,—O—, and —O—C(O)—CH═CH—C(O)—O—; n is greater than 10; x is 2 to 20; andy is at least 1.

In one embodiment, the present disclosure provides a compound of theformula:

wherein: R¹ is selected from H, an alkyl group, an aryl group, andcombinations thereof; R² is R^(f)—Y—(CH₂)_(x)—; R³ is a reactive groupselected from a polymerizable group and a group of formula —W—Si(R⁹)₃;R^(f) is a perfluorinated alkyl group; Y is selected from a bond,—S(O)₂—N(CH₃)—, —S(O)₂—N(CH₂CH₃)—, —S(O)₂—O—, —S(O)₂—, —C(O)—, —C(O)—S—,—C(O)—O—, —C(O)—NH—, —C(O)—N(CH₃)—, —C(O)—N(CH₂CH₃)—, —(CH₂CH₂O)_(y)—,—O—, and —O—C(O)—CH═CH—C(O)—O—; n is an integer of greater than 10; x isan integer from 2 to 20; y is an integer of at least 1; W is an organicgroup; and each R⁹ is independently an alkyl group, aryl group, or acombination thereof, or a hydrolyzable group, wherein at least one R⁹ isa hydrolyzable group.

In one embodiment, the present disclosure provides a compound (i.e., apolymerizable or substrate-reactive polyoxazoline) of the formula:

wherein: R¹ is selected from H, an alkyl group, an aryl group, andcombinations thereof; R² is R^(f)—Y—(CH₂)_(x)—; R³ is a reactive groupselected from a vinyl group, a vinylether group, a (meth)acryloyloxygroup (i.e., an acryloyloxy or methacryloyloxy), a (meth)acryloylaminogroup (i.e., an acryloylamino or methacryloylamino), atrialkoxysilylalkylthio group, and a trialkoxysilylalkylamino group;R^(f) is a perfluorinated (C1-C5)alkyl group; Y is selected from a bond,—S(O)₂—N(CH₃)—, —C(O)—NH—, and —(CH₂CH₂O)_(y)—; n is 20 to 100; x is 2to 20; and y is 1 to 20.

Such compounds are reactive polyoxazolines that can be made usingconventional techniques. An exemplary reaction scheme is shown in theExamples Section (Scheme I). Typically, an oxazoline, particularly a2-oxazoline that includes an R¹ group at the 2-position, is subjected toa ring opening reaction in a suitable solvent (e.g., acetonitrile) inthe presence of an initiator (e.g., methyl trifluoromethansulfonate(i.e., methyl triflate), perfluorobutyl ethylene triflate,perfluorobutyl sulfonamide triflate, methyl toluene sulfonate (i.e.,methyl tosylate), and methyl iodide) with heating (e.g., at atemperature of 80° C.), and subsequently modified to include apolymerizable group (e.g., upon reaction with (meth)acrylic acid) or asubstrate reactive group (e.g., upon reaction with a compound of formulaH—W—Si(R⁹)₃) in the presence of a base (e.g., triethylamine).

The resultant compounds of the present disclosure are useful in makingpolymers suitable for use in making anti-fog, anti-fouling, and/or easyclean coatings. They can be homopolymerized or copolymerized with othermonomers to make suitable coatings. If desired, they can be combinedwith components, such as metal silicates (e.g., lithium silicate), toform hard coatings as is known in the art.

A coating composition can include a solvent. Useful solvents for thecoating compositions include those in which the compound is soluble toat least 1% by weight. Typically, water is used, although other solventssuch as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone,methyl iso-butyl ketone, methyl acetate, ethyl acetate, heptane,toluene, xylene, and ethylene glycol alkyl ether can be used. Thosesolvents can be used alone or as mixtures thereof. The coatingcomposition is typically a homogeneous mixture that has a viscosityappropriate to the application conditions and method. For example, amaterial to be brush or roller coated would likely be preferred to havea higher viscosity than a dip coating composition. The coatingcomposition is typically relatively dilute, often containing at least0.1 wt-%, or at least 1 wt-%, of the compound. Typically, a coatingcomposition includes no greater than 50 wt-%, or no greater than 25wt-%, of the compound.

A wide variety of coating methods can be used to apply a composition ofthe present disclosure, such as brushing, spraying, dipping, rolling,spreading, and the like. The obtained coating on the substrate may becured at room temperature or at an elevated temperature (e.g., 40° C. to300° C.). In some embodiments the curing may be effected by a catalyst(such as an organic or inorganic acid or base, chelate of titanium(e.g., titanium isopropoxide), and tin based compounds (e.g.,dibutyldiacetoxytin), at room temperature or elevated temperatures.

The substrate on which the coating can be disposed can be any of a widevariety of materials. Useful substrates include ceramics, siliceoussubstrates including glass, metal, natural and man-made stone, andpolymeric materials, including thermoplastics and thermosets. Suitablematerials include, for example, poly(meth)acrylates, polycarbonates,polystyrenes, styrene copolymers such as styrene acrylonitrilecopolymers, polyesters, polyethylene terephthalate, silicones such asthat used in medical tubing, paints such as those based on acrylicresins, powder coatings such as polyurethane or hybrid powder coatings,and wood. The substrates can be in the form of wovens, nonwovens, orfilms, for example.

In some embodiments, the substrate is selected to have a group that canreact with the polyoxazoline. For example, the substrate can have aglass or ceramic-containing surface that has silanol groups that canundergo a condensation reaction with group R³ selected from atrialkoxysilylalkylthio or a trialkoxysilylamino group. The product ofthis reaction results in the formation of a —Si—O—Si— bond between thepolyoxazoline and the substrate.

The following is a list of illustrative embodiments of the presentdisclosure.

Embodiment 1 is a compound of the formula:

wherein:

-   -   R¹ is selected from H, an alkyl group, an aryl group, and        combinations thereof;    -   R² is R^(f)—Y—(CH₂)_(x)—;    -   R³ is a reactive group;    -   R^(f) is a perfluorinated alkyl group;    -   Y is selected from a bond, —S(O)₂—N(CH₃)—, —S(O)₂—N(CH₂CH₃)—,        —S(O)₂—O—, —S(O)₂—, —C(O)—, —C(O)—S—, —C(O)—O—, —C(O)—NH—,        —C(O)—N(CH₃)—, —C(O)—N(CH₂CH₃)—, —(CH₂CH₂O)_(y)—, —O—, and        —O—C(O)—CH═CH—C(O)—O—;    -   n is an integer of greater than 10;    -   x is an integer from 2 to 20; and    -   y is an integer of at least 1.

Embodiment 2 is the compound of embodiment 1 wherein R¹ is H, a(C1-C20)alkyl group, a (C6-C12)aryl group, a (C6-C12)ar(C1-C20)alkylgroup, or a (C1-C20)alk(C6-C12)aryl group.

Embodiment 3 is the compound of embodiment 1 wherein R¹ is selected fromH, methyl, and ethyl.

Embodiment 4 is the compound of any one of embodiments 1 through 3wherein the reactive R³ group is a polymerizable group or asubstrate-reactive group.

Embodiment 5 is the compound of embodiment 4 wherein R³ is of theformula —W—Si(R⁹)₃

wherein:

-   -   W is an organic group;    -   each R⁹ group is independently selected from an alkyl group, an        aryl group, a combination thereof, and a hydrolyzable group; and    -   at least one R⁹ is a hydrolyzable group.

Embodiment 6 is the compound of embodiment 4 wherein R³ comprises anethylenically unsaturated group.

Embodiment 7 is the compound of embodiment 4 wherein R³ is selected froma vinyl group, a vinylether group, a (meth)acryloyloxy group, a(meth)acryloylamino group, a trialkoxysilylalkylthio group, and atrialkoxysilylalkylamino group.

Embodiment 8 is the compound of embodiment 7 wherein R³ is selected froma (meth)acryloyloxy group, a (meth)acryloylamino group, atrialkoxysilylalkylthio group, and a trialkoxysilylalkylamino group.

Embodiment 9 is the compound of embodiment 8 wherein R³ is selected froma (meth)acryloyloxy group and a (meth)acryloylamino group.

Embodiment 10 is the compound of any one of embodiments 7 through 9wherein the amide nitrogen of the (meth)acryloylamino group isoptionally substituted with a methyl or ethyl group.

Embodiment 11 is the compound of any one of embodiments 7 through 9wherein the trialkoxysilylalkylamino group is of the formula—N(R)—R⁷—Si(OR⁴)(OR⁵)(OR⁶), wherein R is H, methyl, or ethyl, and eachR⁴, R⁵, and R⁶ is an alkyl group, and R⁷ is an alkylene group.

Embodiment 12 is the compound of any one of embodiments 7 through 9wherein the trialkoxysilylalkylthio group is of the formula—S—R⁸—Si(OR⁴)(OR⁵)(OR⁶), wherein each R⁴, R⁵, and R⁶ is an alkyl group,and R⁸ is an alkylene group.

Embodiment 13 is the compound of any one of embodiments 1 through 12wherein Y is selected from a bond, —S(O)₂—N(CH₃)—, —C(O)—NH—, and—(CH₂CH₂O)_(y)—.

Embodiment 14 is the compound of any one of embodiments 1 through 13wherein R^(f) is a perfluorinated (C1-C5)alkyl group.

Embodiment 15 is the compound of embodiment 14 wherein R^(f) is aperfluorinated C4 alkyl group.

Embodiment 16 is the compound of any one of embodiments 1 through 15wherein n is an integer no greater than 500.

Embodiment 17 is the compound of embodiment 16 wherein n is an integerfrom 20 to 100.

Embodiment 18 is the compound of any one of embodiments 1 through 17wherein x is from 2 to 10.

Embodiment 19 is the compound of embodiment 16 wherein x is an integerfrom 2 to 6.

Embodiment 20 is the compound of any one of embodiments 1 through 19wherein y is an integer no greater than 20.

Embodiment 21 is the compound of embodiment 18 wherein y is an integerfrom 1 to 5.

Embodiment 22 is a compound of the formula:

wherein:

-   -   R¹ is selected from H, an alkyl group, an aryl group, and        combinations thereof;    -   R² is R^(f)—Y—(CH₂)_(x)—;    -   R³ is selected from a vinyl group, a vinylether group, a        (meth)acryloyloxy group, and a (meth)acryloylamino group, a        trialkoxysilylalkylthio group, and a trialkoxysilylalkylamino        group;    -   R^(f) is a perfluorinated (C1-C5)alkyl group;    -   Y is selected from a bond, —S(O)₂—N(CH₃)—, —C(O)—NH—, and        —(CH₂CH₂O)_(y)—;    -   n is an integer from 20 to 100;    -   x is an integer from 2 to 20; and    -   y is an integer from 1 to 20.

Embodiment 23 is the compound of embodiment 22 wherein R³ is apolymerizable group selected from a (meth)acryloyloxy and a(meth)acryloylamino.

EXAMPLES

Objects and advantages of this disclosure are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this disclosure.

General Procedures for Polymer Synthesis:

Glassware was dried overnight in an oven at 150° C. prior to use.Reagents were purchased from Fisher Scientific or Sigma Aldrich.Acetonitrile was anhydrous grade. Methyl iodide, methyl tosylate, andoxazoline monomers were distilled over CaH₂ and stored over 3 Åmolecular sieves. Other reagents for oxazoline polymerization werestored over 3 Å molecular sieves prior to use. Solvents were removed

Scheme I: General scheme for the synthesis of poly(oxazoline) polymers(wherein “LG” = leaving group, and the * represents the point ofattachment of the group)

R¹ R² LG R³ *—H R^(f)—Y—(CH₂)_(x)—* *—I

*—CH₃

*—CH₂CH₃

*—S—(CH₂CH₂CH₂)—Si(OR⁴)(OR⁵)(OR⁶) *—NR—(CH₂CH₂CH₂)—Si(OR⁴)(OR⁵)(OR⁶) (R= H, Me = Et)

R^(f)—Y:

Preparatory Example 1 Synthesis of R²-LG

A round bottom flask, equipped with a stopcock, was purged withnitrogen, then charged with anhydrous dichloromethane (20 milliliters(mL)), 1,4-dioxane (20 mL), pyridine (2.0 grams (g), 24.6 millimoles(mmol)) and 1H, 1H, 2H, 2H-perfluorohexanol (5.0 g, 18.9 mmol). Thesolution was cooled to 0° C., then trifluoromethanesulfonic anhydride(7.0 g, 24.6 mmol) was added drop-wise by syringe to the vigorouslystirring solution. After stirring for 2 hours at 0° C., the solution wasslowly warmed to room temperature and then stirred for additional 10hours. The resulting suspension was filtered to remove the precipitatedsalts. The solution was then washed successively with 1 Normal (N) HCl,saturated NaHCO₃, 10% copper sulfide solution, and brine. The organicphase was dried over anhydrous Na₂SO₄ and excess solvent was removedunder vacuum. The resulting brown oil was distilled under reducedpressure to yield 3.0 g of the product as colorless liquid.

Preparatory Example 2 Synthesis of R²-LG

A round bottom flask, equipped with a stopcock, was purged withnitrogen, then charged with anhydrous dichloromethane (50 mL),1,4-dioxane (50 mL), pyridine (3.6 g, 45.4 mmol) andN-methyl-1,1,2,2,3,3,4,4-nonafluoro-N-(2-hydroxyethyl)butane-1-sulphonamide(12.5 g, 34.9 mmol). The solution was cooled to 0° C., thentrifluoromethanesulfonic anhydride (12.8 g, 45.4 mmol) was addeddrop-wise by syringe to the vigorously stirring solution. After stirringfor 2 hours at 0° C., the solution was slowly warmed to room temperatureand then stirred for additional 10 hours. The resulting suspension wasfiltered to remove the precipitated salts. The solution was then washedsuccessively with 1N HCl, saturated NaHCO₃, 10% copper sulfide solution,and brine. The organic phase was dried over anhydrous Na₂SO₄ and excesssolvent was removed under vacuum. Recrystallization of the resultingsolid from cold toluene yielded 7.5 g of the product as white solid.

Example 1 Synthesis of Polymerizable Polyoxazoline

A 3-necked flask with attached condenser and stopcock was purged withnitrogen, then charged with acetonitrile (20 mL) and perfluorobutylethylene triflate (R²-LG) initiator of Preparatory Example 1 (0.4 g, 1.0mmol). The solution was cooled to 0° C., then 2-methyl-2-oxazoline (2.6g, 30 mmol) was added by syringe. After stirring for 2 hours whileslowly warming to room temperature, the solution was heated to 80° C. inan oil bath, then stirred for 20 hours. After cooling to roomtemperature, acrylic acid (0.36 g, 5.0 mmol) and triethylamine (0.61 g,6.0 mmol) were added by syringe in that order. The solution was heatedback up to 80° C., and stirred for another 24 hours. After cooling, thesolution was filtered, then added dropwise with vigorous stirring to 200mL of diethyl ether to precipitate the polymer. The resulting suspensionwas stirred for 15 minutes (min). The precipitate was isolated byfiltration, washed with diethyl ether, and dried under vacuum at 80° C.overnight, yielding 2.6 g of white solid. End-group analysis by ¹H-NMRspectroscopy showed that polymer with n=30 was obtained.

Example 2 Synthesis of Polymerizable Polyoxazoline

A 3-necked flask with attached condenser and stopcock was purged withnitrogen, then charged with acetonitrile (15 mL) and perfluorobutylsulfonamide triflate (R²-LG) initiator of Preparatory Example 2 (0.74 g,1.5 mmol). The solution was cooled to 0° C., then 2-methyl-2-oxazoline(3.9 g, 46 mmol) was added by syringe. After stirring for 15 minutes,the solution was warmed to 80° C., then stirred for 16 hours. Aftercooling to room temperature, acrylic acid (0.16 g, 2.3 mmol) andtriethylamine (0.31 g, 3.0 mmol) were added by syringe in that order.The solution was heated back up to 80° C., and stirred for another 4hours. After cooling, the acetonitrile was evaporated with a stream ofnitrogen, and the remainder was dissolved in 50 mL of chloroform. Thissolution was filtered, then concentrated to about 20 mL. The solutionwas then added dropwise, with vigorous stirring, to 200 mL of diethylether to precipitate the polymer. The resulting suspension was left inthe freezer overnight. The precipitate was isolated by filtration,washed with diethyl ether, and dried under vacuum at 80° C. overnight,yielding 4.7 g of white solid. Accounting for the presence oftriethylammonium triflate impurities, the yield was 96%. End-groupanalysis by ¹H-NMR spectroscopy showed that polymer with n=30 wasobtained.

Example 3 Synthesis of Alkoxysilane-Functional Polymer

A 3-necked flask with attached condenser and stopcock was purged withnitrogen, then charged with acetonitrile (5 mL) and perfluorobutylsulfonamide triflate initiator (R²-LG) initiator of Preparatory Example2 (0.63 g, 1.3 mmol). The solution was heated to 40° C., then2-methyl-2-oxazoline (3.3 g, 39 mmol) was added by syringe. Afterstirring for 15 minutes, the solution was warmed to 80° C., then stirredfor 17 hours. After cooling to 0° C., (3-mercaptopropyl)trimethoxysilane(0.30 g, 1.6 mmol) and triethylamine (0.26 g, 2.6 mmol) were added bysyringe in that order. The solution was heated back up to 80° C., andstirred for another 2 hours. After cooling, the acetonitrile wasevaporated with a stream of nitrogen, and the remainder was dissolved in50 mL of chloroform with 2.5% methanol. This solution was filtered, thenconcentrated to about 20 mL. The solution was then added dropwise withvigorous stirring to 200 mL of diethyl ether containing 2.5% methanol.The resulting suspension was left in the freezer overnight. Theprecipitate was isolated by filtration, washed with diethyl ether, anddried under vacuum at 80° C. overnight, yielding 4.0 g of white solid.Accounting for the presence of triethylammonium triflate impurities, theyield was close to quantitative. End-group analysis by ¹H-NMRspectroscopy showed that polymer with n=30 was obtained.

Example 4 Preparation and Characterization of Coatings

The polymer of Example 3 was dissolved in water at a concentration of10% by weight. This solution was mixed in varying ratios with an aqueoussolution of lithium silicate (Nissan Chemical Industries) diluted to aconcentration of 10% by weight. These solutions were then coated on 2mil polyethylene terephthalate (PET) film with a number 12 wire-woundrod (BYK instruments). The films were dried and cured in an oven at 80°C. for 1 hour.

Coatings were characterized by dynamic contact angle and by measuringtransmission and haze. Dynamic contact angle measurements were observedusing a DSA 100 video contact angle goniometer (Kruss Inc.) equippedwith a Hamilton syringe having a flat-tipped needle. Deionized water andn-hexadecane were used as the probe fluids. Advancing contact angle andreceding contact angle were measured as water was supplied via thesyringe into or out of sessile droplets (drop volume approximately 5microliters (μL)). All reported values are averages of six contact anglemeasurements of drops on three different areas of each sample (left andright angles measured for each drop). Reported errors are one standarddeviation. Percent (%) Transmission and % Haze were measured for coatedfilms using a Haze-gard plus (BYK Instruments Inc.). Measurements werecollected on three different areas of each sample and reported errorsare one standard deviation. The results are summarized in Table 1 below.

TABLE 1 Optical and Surface Properties of Coated PET Film Ratio ofOptical Properties Contact Angles Polymer to % Trans- Water WaterHexadecane Hexadecane Lithium Silicate mission % Haze Advancing RecedingAdvancing Receding 1:4 84.7 ± 1.3 32.4 ± 1.2  wets wets wets Wets 1:291.9 ± 0.1 12.80 ± 0.78  23.0 ± 1.8 12.6 ± 0.8 wets Wets 1:1 91.6 ± 0.21.73 ± 0.14 27.5 ± 1.1 13.2 46.7 ± 0.6 27.2 ± 0.5 2:1 91.4 ± 0.3 2.25 ±0.87 34.3 ± 4.4 20.6 ± 0.9 46.8 ± 0.7 20.2 ± 0.8 4:1 91.2 ± 0.1 1.80 ±0.01 46.6 ± 0.7 14.2 ± 0.7 45.8 ± 0.9 32.2 ± 0.4

Example 5 Anti-Fog Properties

The anti-fog properties of the coatings prepared in Example 4 wereassessed via the following test. In a 1000 mL covered beaker, 400 mL ofwater was heated to 80° C. The lid contained a circular cut opening of 4cm diameter, which was covered with a metal plate. The plate wasremoved, and the film sample was immediately placed over the openingwith the coated side down. The degree of fogging observed on the filmwas recorded initially (within moments of applying the film), after 30seconds (sec), and after 60 sec. The degree of fogging was graded byassigning one of the following ratings: P=pass (the film remainscompletely transparent), SF=slight fail (water droplights reducevisibility through the film slightly), F=fail (significant loss ofvisibility through the film), or BF=big fail (the film is renderedopaque with fog). The results are shown in Table 2.

TABLE 2 Fogging Properties of Coated PET Films Ratio of Polymer FoggingFogging to Lithium Initial After After Silicate in Coating Fogging 30Sec 60 Sec 1:4 F P P 1:2 SF P P 1:1 F SF SF 2:1 SF P P 4:1 P P P NoCoating BF BF BF

The complete disclosures of the patents, patent documents, andpublications cited herein are incorporated by reference in theirentirety as if each were individually incorporated. Variousmodifications and alterations to this disclosure will become apparent tothose skilled in the art without departing from the scope and spirit ofthis disclosure. It should be understood that this disclosure is notintended to be unduly limited by the illustrative embodiments andexamples set forth herein and that such examples and embodiments arepresented by way of example only with the scope of the disclosureintended to be limited only by the claims set forth herein as follows.

1. A compound of the formula:

wherein: R¹ is selected from H, an alkyl group, an aryl group, andcombinations thereof; R² is R^(f) Y—(CH₂)_(x)—; R³ is a reactive group;R^(f) is a perfluorinated alkyl group; Y is selected from a bond,—S(O)₂—N(CH₃)—, —S(O)₂—N(CH₂CH₃)—, —S(O)₂—O—, —S(O)₂—, —C(O)—, —C(O)—S—,—C(O)—O—, —C(O)—NH—, —C(O)—N(CH₃)—, —C(O)—N(CH₂CH₃)—, —(CH₂CH₂O)_(y)—,—O—, and —O—C(O)—CH═CH—C(O)—O—; n is an integer of greater than 10; x isan integer from 2 to 20; and y is an integer of at least
 1. 2. Thecompound of claim 1 wherein R¹ is selected from H, methyl, and ethyl. 3.The compound of claim 1 wherein R³ is a polymerizable group and/or asubstrate-reactive group.
 4. The compound of claim 1 wherein R³ isselected from a vinyl group, a vinylether group, a (meth)acryloyloxygroup, a (meth)acryloylamino group, a trialkoxysilylalkylthio group, anda trialkoxysilylalkylamino group.
 5. The compound of claim 1 wherein Yis selected from a bond, —S(O)₂—N(CH₃)—, —C(O)—NH—, and —(CH₂CH₂O)y-. 6.The compound of claim 1 wherein R^(f) is a perfluorinated (C1-C5)alkylgroup.
 7. The compound of claim 1 wherein n is an integer no greaterthan
 500. 8. The compound of claim 1 wherein n is an integer from 20 to100.
 9. The compound of claim 1 wherein x is an integer from 2 to 10.10. The compound of claim 1 wherein y is an integer no greater than 20.11. A compound of the formula:

wherein: R¹ is selected from H, an alkyl group, an aryl group, andcombinations thereof; R² is R^(f) Y—(CH₂)_(x)—; R³ is selected from avinyl group, a vinylether group, a (meth)acryloyloxy group, and a(meth)acryloylamino group, a trialkoxysilylalkylthio group, and atrialkoxysilylalkylamino group; R^(f) is a perfluorinated (C1-C5)alkylgroup; Y is selected from a bond, —S(O)₂—N(CH₃)—, —C(O)—NH—, and—(CH₂CH₂O)_(y)—; n is an integer from 20 to 100; x is an integer from 2to 20; and y is an integer from 1 to
 20. 12. The compound of claim 3,wherein R³ is of the formula —W—Si(R⁹)₃ wherein: W is an organic group;each R⁹ group is independently selected from an alkyl group, an arylgroup, a combination thereof, and a hydrolyzable group; and at least oneR⁹ is a hydrolyzable group.
 13. The compound of claim 3, wherein R³comprises an ethylenically unsaturated group.
 14. The compound of claim3, wherein R³ is selected from a vinyl group, a vinylether group, a(meth)acryloyloxy group, a (meth)acryloylamino group, atrialkoxysilylalkylthio group, and a trialkoxysilylalkylamino group. 15.The compound of claim 14, wherein the trialkoxysilylalkylamino group isof the formula —N(R)—R⁷—Si(OR⁴)(OR⁵)(OR⁶), wherein R is H, methyl, orethyl, and each R⁴, R⁵, and R⁶ is an alkyl group, and R⁷ is an alkylenegroup.
 16. The compound of claim 14, wherein the trialkoxysilylalkylthiogroup is of the formula —S—R⁸—Si(OR⁴)(OR⁵)(OR⁶), wherein each R⁴, R⁵,and R⁶ is an alkyl group, and R⁸ is an alkylene group.
 17. The compoundof claim 11, wherein R³ is a polymerizable group selected from a(meth)acryloyloxy and a (meth)acryloylamino.